Metallized monoazo dyestuffs containing a polyhalogenopyrimidyl radical



and Y being a member selected from the group United States Patent 0 METALLIZED MONOAZO DYESTUFFS CONTAIN- ING A POLYHALOGENOPYRIMIDYL RADICAL Jakob Benz, Oberwil, Basel-Land, and Hanspeter Uehlinger, Basel, Switzerland, assignors to Sandoz Ltd.- (also known as Sandoz A.G.), Basel, Switzerland No Drawing. Filed July 1, 1963, Ser. No. 292,158 Claims priority, application Switzerland, Apr. 10, 1959, 71 8 f 4 9 Claims. (cl. 260-146) This application is a continuation-in-part of our'application Ser. No. 20,845, filed April 8, 1960 and now abandoned and relates to the lz2-chromium and-lz'2- cobaltcomplex compounds of the monoazo dyestufis of the formula i '1 a e w (so a) wherein X represents the polyhalogenopyrirnidyl"radical hal being a halogen atom with an atomic number from 17 to 35, inclusive, i.e. being chlorine or bromine, was n of hydrogen, chlorine and bromine, n represents one of the integers 1 and 2,; I the nucleus A may bear any desired substituentsaeircept sulfonic acid groups, 7 v

the group I G t NHX I/TI. i' stands in one of the positions 7 and 8 of the naph thalene nucleus and the group NH- stands in one of the positions 3 and 4.

A series of particularly interesting dyestuffs comprises pounds of the dyestutfs of the formula o her wherein V v .7

'hal is a halogen atom'with an atomic numb'er from "'17 to 35, inclusive, i.e. is chlorine or bromine; Y is hydrogen, chlorine or bromine,

R is chlorine or nitro,

and

R is hydrogen, chlorine. or nitro and is ditferent fromLR 3,288,776 Patented Nov. 29, 1966 ice 1 mole of a coupling component of the formula wherein n possesses the afore-cited meaning, and H represents an exchangeable hydrogen atom, and 1 mole of a 2 4,6-trihalogeno or 2,4,5,6-tetrahalogenopyrimidine, the reaction being conducted in such a manner that the dia zo compound. is introduced into the position ortho to OH of the coupling component andthe polyhalogenopyrimidyl radical (II) replaces the'hydrogen atom H of the coupling component; during or after the formation of the dyestutfs A: they aretr'eated with a chromium-or cobalt-yielding "-caj @uan the 1:2-chromium and the 1:2-cobalt complex comagent. I

A suitabl lprocedure is as follows: 1 mole of a mono- ,azo'dyestutf of the formula m NH-- 00 H a; U) n-'l .iii hierein" A,1I'-l1 and'n have the afore-cited meanings, lmole ,of a '2,4, 6-t'rihalogeno-f or 2,4,5,6-tetrahalogenopyrimidine,

andla ,chro'rnium or cobalt-yielding agent are reacted with .each other' so'thajt the2,4,6;-trihalogenoor 2,4,5,6-tetra- .halogenopyrimidine reacts with the exchangeable hydro- 'gen' ,atorr'i of the monoazo dyestuff (IV) and the chromidihydroiryazo' grouping;

"fiArnodification of this procedure consists in coupling in rum-f or cobalt-yielding agent reacts with the ortho-orthofortho pojsition'tothe hydroxy group 1 mole of the diazo compound of an amine of the formula fwhere'in n and X possess the above-named meanings,

"andtreatin g the resulting monoazo dyestuff with a chro- The metal-containing reactive dyestuifss obtained by both procedures are the 1:2-chromium or 1:2-cobalt com- The process for the production of the new chrom'iur nwith each other 7 n l moleof the diazo compound of 'a Z-aminorI-hydr irybenzene which may contain any desired substituents except sulfonic acid groups,

. or cobalt-containing reactive dyestutfs consistsin reacting plex compounds of the monoazo dyestuifs of Formula I.

'The substituents Which, in accordance With the definition,

may be contained in the nucleus A are halogen (chlorine,

bromine) atoms, lower alkyl'or alkoxy groups (methyl, ethyl, methoxy, ethoxy), nitro groups, acylamino i(acetyl-,

propionyl, benzoyl-, carbomethoxy-, carbethoxyamino) groups, alkylsulfonyl (methyl'sulfonyl) andsulfonic acid amide groups which may --be substituted on the nitrogen atom (amide; methyla'r'nide, ethyl'amide,- 'dimethylamide,

' die thylamide, 2 hydroxyethylamide,. .di (2' hydroxyethyl)-amide, 2- or 3-hydroxypropylamide, S-methoxypropylamide, 3- or 4-methox'ybutylamide, Z-ethoxyethyhsulfonic acids, 2-amino-8-hydroxynaphthalene-3.6-disulfonic acid, and the derivatives of these acids in which the amino group is acylated by an aminobenzoyl radical.

The polyhalogenopyrimidyl radical X is the radical condensed in one of the positions 2 and 4 of 2,4,6-tribromoor 2,4,5,G-tetrabromopyrimidine or preferably'of 2,4,6- 1

trichloro-, 2,4,5,6-tetrachloro-- or 2,4,6-trichloro-5-bromopyrimidine.

The reaction of the monoazo dyestufi's of Formula or their chromium or cobalt complex compounds with the polyhalogenopyrimidines is carried out in aqueous medium. The halide can be employed as such or in solution in an organic solvent; solvents especially suitable for this purpose are acetone, benzene, chlorobenzene and toluene.

The reaction temperature is varied to suit the reactivity of the individual starting products and may range from e.g. 20 to 100 C. If temperatures higher than about 40 C. are necessary, it is advisable to work in vessels equipped with reflux condensers because of the volatility in steam of the polyhalogenopyrimidines.

The reaction may be conducted in weakly alkaline,

or, alternatively, sodium or potassium carbonate or bii The coupling of the diazo compound of an amine of the Formula V with a coupling component of the Formula VI is carried out in alkaline medium, preferably at temperatures of 0-20 C.

The monoazo dyestuffs are converted into their 1:2-

chromium or 1:2-cobalt complex compounds preferably 1 in aqueous solution or in an organic medium, e.g. formamide, or in the concentrated aqueous solution of an alkali metal salt of a low molecular aliphatic monocarboxylic acid. It is of advantage to proportion the reactants so that an amount of metal-yielding agent containing less than two but at least one atom of metal acts upon two molecules of the monoazo dyestnif.

Suitable chromium compounds are e.g. chromic fluoride, chromic sulfate, chromic formate, chromic acetate, chromic potassium sulfate or chromic ammonium sulfate. The chromates e.g. sodium or potassium chromate or bichromate, are also eminently suitable for metallizing the monoazo dyestulfs. It is advantageous to work here in a strongly caustic alkaline medium, to which reducing substances may be added if desired.

Cobaltous formate, cobaltous acetate and cobaltous sulfate are examples of suitable cobalt compounds. If metall lation is effected in the concentrated aqueous solution of an alkali metal salt of a low molecular aliphatic monocarboxylic acid, water-insoluble metal compounds can be used, e.g. cobalt hydroxide or cobalt carbon-ate.

It is especially advantageous to carry out metallization in aqueous or alkaline medium to which the metal compounds are added in presence of compounds which maintain the metal dissolved in complex combination in caustic dark blue and black shades.

alkaline medium; examples of such compounds are tartaric acid, citric acid and lactic acid.

The metal complex compounds obtained are precipitated from aqueous medium by the addition of salt, if desired after running the organic metallizing solution into brine, and are subsequently filtered off, washed if necessary and dried.

The metal-containing azo dyestuffs thus obtained are homogeneous metal complex compounds in which essentially one atom of metal is linked to two molecules of the monoazo compound. The metal complex compounds are so-called 1:2 complexes in which one molecule of the monoazo compound is linked with approximately 0.3 to 0.7 atom of metal.

:The dyestuifs of the invention possess good solubility in water, good stability in printing pastes and padding liquors, good compatibility to salts and hard water; they 7 are practically insensitive to heavy metals such as iron,

copper or chromium and reserve cellulose-2 /2-and-triacetate, polyester fibers such as polyethylene terephthalate, polyvinyl chloride and polyvinyl acetate fibers, pure poly-acrylonitrile fibers and polyalkylene fibers such as polyethylene and polypropylene fibers.

They posses a very good reactivity with vegetable fibers, e.g. cotton and linen, regenerated cellulose, e.g. viscose filament fibers, viscose staple fibers, cuprammonium rayon; animal fibers such as'wool and silk and synthetic polyamide fibers such as nylon 6,6, nylon 6 and nylon 11. Therefore they are suitable for dyeing leather, for dyeing, padding or printing wool, silk, synthetic polyamide fibers, and fibers of natural and regenerated cellulose and mixtures of these fibers in violet,

The commonly used padding and printing techniques can be applied, e.g. the padding processes: Pad Jig, Pad Steam, Pad Roll, Pad Batch and therrnofixation process, and the printing processes named rollerprinting, screen printing, emulsion printing-and vigoureux printing; in these printing processes the dyestuffs are fixed on the substrate by steaming or thermofixation.

The optimum conditions of application of the dyestulfs vary widely depending on the type of fiber to be dyed. In the case of animal fibers and synthetic polyamide fibers it is preferable to dye, pad or print, or alternatively to fix, in a weakly acid, neutral or weakly alkaline medium, e.g. in presence of acetic acid, formic acid, ammonium sulfate, sodium acetate, sodium bicarbonate, sodium or .potassium carbonate, sodium meta-phosphate, etc. Dyeing can also be carried out in an acetic acid to neutral bath in presence of levelling agents, e.g. polyoxethylated fatty amines or mixtures of the same with alkylpolyglycol ethers, the dyebath being adjusted on completion of dyeing to a neutral or Weakly alkaline reaction, using for this purpose small amounts of an agent of alkaline reaction, e.g. ammonia, sodium bicarbonate, carbonate or hydroxide, etc., or compounds which react alkaline on heating, e.g. hexamethylenetetramine or urea. The dyed goods are then thoroughly washed and if necessary acidified with a little acetic acid.

The dyeings and prints on wool, silk and synthetic polyamide fibers possess good fastness to light, washing, water, sea water, milling, acid and alkaline perspiration, crocking, chlorinated swimming pool Water, hypochlorites, peroxides, ironing, acids (dilute acetic acid, dilute tartaric acid in the cold), alkali (sodium bicarbonate, sodium carbonate), gas fumes and organic solvents.

Cellulosic fibers are dyed, padded and printed preferably from alkaline media, e.g. in presence of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium meta-silicate, sodium borate, water glass, *trisodium phosphate, ammonia, trirnethylamine, quaternary bases, e.g. tetra-alkylammonium compounds, etc. To prevent reduction ream tions during dyeing, padding or printing, it is often advantageous to use a mild oxidizing agent, e.g. sodium l-nitrobenzene-3-sulfonate. Dyeings on cellulosic fibers are normally fixed by treatment in heat. Provided sufficiently strong alkalis such as sodium or potassium hydroxide, sodium metasilicate or trisodium phosphate are used, a number of the dyestuffs can be applied by cold dyeing methods.

In dyeing, padding and printing applications the dyestutfs can be fixed simultaneously or subsequently, in the same or in a fresh bath, if necessary after intermediate drying. When fixation is carried out in a fresh bath it is advisable to include in it a water-soluble salt, e.g. sodium sulfate, to preclude a partial re-dissolving of the dyestuff in the liquor. After fixation the portion of unreacted dyestuif, i.e. the dyestufi which has not taken part in the chemical reaction with the fiber, must be removed from the dyed or printed mate-rial. Owing to the very slight substantivity and the good solubility in Water of the new dyestuffs this removal is in general easy and can often be carried out by rinsing with hot water, whereby in case of prints no staining of the unprinted areas appears. Washing -at higher temperatures with solutions of soap or of synthetic detergents, e.'g. alkylarylsulfonates such as sodium dodecylbenzenesulionate, alkyl sulfates such as sodium dodecyl, oleyl or cetyl sulfate, optionally sulfated or carboxyrnethylated alky-lpolyglycol, monoor dialkylphenylpolyglycol ethers, although it is seldom necessary, is nevertheless generally employed in routine padding and printing processes in order to obtain perfect prints and dyeings.

The dyein-gs and prints on cellulosic fibers possess good fastness to light, gas fumes and hypochlorites, and excellent 'fastness to water, sea water, Washing, soda boiling, acid and alkaline perspiration, erocking, ironing and or ganic solvents (alcohols, ketones, esters, aromatic and aliphatic hydrocarbons which may be halogenated, pyridine and lzl-pyridine-water mixture, dimethylformamide, dimethylsul'foxide, etc.), these excellent fastness properties being due to the stable chemical linkage formed between the dyestutf molecule and the cellulose molecule. In addition the dyein-gs and prints are also very fast to acids (cold dilute acetic and tartaric acid), alkali (sodium bicarbonate and carbonate) peroxides and chlorinated swimming pool water and are, very suitable for anticrease treatments (i.e. the antiorease finishing treatment does not affect the fastness to light).

In the following examples the parts and percentages are by weight and the temperatures in degrees Centigrade.

EXAMPLE 1 31.9 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 160 parts of water by the addition of dilute sodium hydroxide solution at 60 and a pH value of 48-50 With vigorous stirring 21.8 parts of 2.4.5 .6-tetrachloropyrimidine are added, then the reaction medium is heated at 60 for 56 hours, during which time its pH is maintained at 4.0-4.2 by dropping in a dilute sodium carbonate solution. On completion of condensation the reaction mass is brought to a temperature of 20 by external cooling and 10.6 parts of sodium carbonate in 50 parts of water are added. Over the next minutes this solution is run into a suspension obtained by diazotization of 14.4 parts of 2-amino-l-hydroxy-4- chlorobenzene and neutralized to Congo with sodium carbonate. After stirring overnight at about the monoazo dyestuff is filtered off and the residue washed with water. The dyestuff paste is suspended in 500' parts of water at 80 and at this temperature 16 parts of cobaltous sulfate heptahydrate are added. The temperature is subsequently maintained at 94-97 for 2% hours, a constant pH of 5.0-6.0 being maintained by dropwise addition of a dilute sodium carbonate solution. The dyestufi is precipitated by the addition of sodium chloride,

filtered off, dried at 70 and ground to give a dark powder which dissolves in water with a blue coloration.

6 Mercerized cotton sateen is printed with a paste of the following composition:

50 parts of the dyestuff obtained according to the foregoing details 100 parts of urea 375 parts of water 450 parts of a 3% sodium alginate thickening 10 parts of sodium 1-nitro benzene-3-sulfonate 15 parts of sodium carbonate 1000 parts The print is dried, steamed for 10-15 minutes at 102- 104, rinsed in cold and warm water, soaped at the boil, rinsed again and dried. It is of a reddish navy blue shade possessing good light and wet fastness.

The dyest uff can also be fixed on the fiber by treatment in dry heat for about 5 minutes at 140-150 or for about 1 minute at 200 C. Since the dyestuifis practically nonsubstantive and Well soluble in Water, the non-fixed por tion can also be removed in-the following manner:

The fixed print is washed for 5 minutes in cold water at a :goods-to-liquor ratio of 1:40, then put into anew cold Water bath (goods-to-liquor ratio of p 1:40) which is heated to 100 in the course of 5 minutes and held at 100 C. for 5 minutes, The Washed print is withdrawn, rinsed with running tap water and dried. The navy blue print is fast to light and to wet treatments and the unprinted area is perfectly white.

EXAMPLE 2 51.7 parts of the dyestufi (as the disodium salt) from diazotized 2-amino-1-hydroxy-4-chlorobenzene and l-amino- 8-hydroxynaphthalene-3.6-disulf0n'ic acid arestirred into 300 parts of water. At 30 parts of crystallized sodium acetate and 30 parts of crystallized ch'rlomic potassium sulfate are added and the mixture is heated for- 24 hours with refi-ux. Subsequently the dyestuff solutionis cooled to 80, 21.8 parts of 2.4.5.6-tetrachloropyrimidine are added and it is stirred for a .few hours at 80 with dropwise addition of dilute sodium carbonate solution to maintain the pH value at 5. On completion of condensation the dyestuit is precipitated at 80 by the addition of sodium chloride and filtered off, dried and ground. It is a black powder which dissolves in water to give dark blue solutions.

A cotton fabric is impregnated on a pad with a solution of 8 parts of the above-described dyestuif, 20 parts of urea, 2 parts of sodium carbonate and parts of water,

passed between squeeze rollers to give an increase of about 70% on its dry weight and then dried. The dyeing is fixed by treatment in dry heat for 4-5 minutes at rinsed cold and warm, soaped at the boil fior 15 minutes with a 0.2% solution of a non-ionic detergent, and finally rinsed and dried. A navy blue shade fast to boiling is obtained.

For the vigoureux printing of wool a paste of the following composition is used:

60 parts of the dyestuff obtained according to the foregoing details 200 parts of urea 535 parts of water 200 parts of 3% sodium alginate thickening 3 parts of a highly sulfonated castor oil 1000 parts hours at 25".

p The printed slubbing is steamed for two 45-minute periods with intermediate cooling. It is then rinsed with hot and cold water and dried. The obtained navy blue print is fast to light and to wet treatments.

EXAMPLE 3 52.8 parts of the monoazo dyestuff (as the disodium salt) of diazotized Z-amino-l-hydroXy-4-nitrobenzene and 1-amino-8-hydroxynaphthalene-3.6-disulfonic acid are suspended in 300 parts of Water at 75. A solution of 14.5 parts of cobaltous sulfate heptahydrate in 40 parts of water is dropped into the suspension in the course of 30 minutes and at the same time a dilute sodium carbonate solution is dropped in to maintain the pH value of the reaction mass between 5.0 and 6.0. After the addition of the cobaltous sulfate solution the mass is stirred for a further hour at 75, after which the dyestuff is precipitated with sodium chloride and filtered 011'.

The cobalt complex compound is dissolved in 300 parts of water and at 80 22 parts of 2.4.5 .6-tetrachloropyrimidine are added. The pH value of the reaction solution is maintained between 3.0 and 4.0 by dropwise addition 'of 'a dilute sodium carbonate solution. After stirring for several hours at 80 condensation is completed. By the addition of sodium chloride the dyestuif is precipitated and is then filtered off and dried in vacuo. It is a dark powder which dissolves in Water with a reddish black coloration.

Cotton cretonne is printed with a paste of the following composition:

1000 parts The printed fabric is dried, steamed for minutes at 102-104", rinsed in cold and warm water, soaped at the boil, rinsed again and dried. A reddish black print with good light and wet fastness is obtained.

Pad Batch dyeing method Mercerized cotton sateen is impregnated at 25 with a padding liquor containing per liter:

50 grams of the above-described dyestuflf 150 grams of calcined sodium sulfate 30 grams of sodium metasilicate 20 grams of a 30% sodium hydroxide solution.

The impregnated material is squeezed so that the pickup of liquor is about 75% of the Weight of the dry material, Wrapped in a sheet of plastic and stored for 48 It is then rinsed with cold and with hot water, soaped for minutes at the boil with a solution containing 0.3 gram of a carboxymethylated alkylpolyglycol ether and 0.5 gram of sodium carbonate per liter, rinsed again and dried. The obtained black dyeing is fast to light and to wet treatments.

EXAMPLE 4 52.8 parts of the monoazo dyestuff (as the disodium salt) from diazotized Z-amino-l-hydroXy-4-nitrobenzene and Z-amino-8-hydroxynaphthalene-3.6-disulfonic acid are metallized with cobaltous sulfate according to the details of Example 3.

The cobalt complex compound is dissolved in 300 parts of Water. To the solution heated at 18.3 parts of 2.4.6-tri-chloropyrimidiue are added and a 20% sodium carbonate solution is dropped in so that the pH-value is maintained between 4 and 5. When the condensation is completed the dyestuff is precipitated by means of sodium chloride, filtered off, dried and ground. It is a dark powder which dissolves in Water with a brownish violet coloration. Mercerized cotton sateen is printed with a paste of the following composition:

50 parts of the dyestuif obtained according to the foregoing details 100 parts of urea 368 parts of water 450 parts of a 3% sodium alginate thickening 20 parts of potassium carbonate 2 parts of a 30% sodium hydroxide solution 10 parts of sodium 1-nitrobenzene-3-sulfonate 1000 parts The dried print is steamed for 10-15 minutes at 102- 104 and subsequently rinsed in cold and warm water, soaped at the boil, rinsed again and dried. A violet print with good light and wet fastness is obtained.

EXAMPLE 5 56.3 parts of the dyestuff (in the form of the disodium salt) obtained by coupling diazotized Z-amino-l-hydroxy- 4-chloro-5-nitrobenzene with 1-amino-8-hydroxynaphthalene-3.6-disulfonic acid in alkaline medium are stirred into 400 parts of water. The dyestulf suspension is adjusted to a pH value of 5 and after the addition of 18.3 parts of 2.4.6-trichloro-pyrimidine it is stirred for-a few hours at the pH value of the reaction mixture being maintained at 5 by dropwise addition of dilute sodium carbonate solution. When condensation is completed the dyestutf suspension is stirred with 35 parts of crystallized sodium acetate and 16 parts of cobaltous sulfate heptahydrate at until the formation of the metal complex is completed. In the course of metallization the dyestuff goes into solution. By slow addition of sodium chloride at 80 the dyestuff is precipitated and is then filtered off, dried and ground to give a black powder which dissolves in water with a dark blue coloration.

Viscose staple fiber is printed with a paste of the following composition:

60 parts of the dyestuff obtained according to the above details 200 parts of urea 265 parts of water 450 parts of 4% sodium alginate thickening 10 parts of sodium 1-nitrobenzene-3-sulfonate 15 parts of sodium carbonate 1000 parts The print is dried and treated in dry heat for l minute at 200 or 10 minutes at then rinsed in cold and warm Water and soaped at the boil. After further rinsing and drying a reddish navy blue print of good light and wet fastness is obtained.

The following table gives details of further chromiumor cobalt-containing reactive dyestuifs which were obtained according to the details of Examples 1 to 5. In the table they are characterized by the diazo and coupling components in columns (I) and (II), by the polyhalogenopyrimidine used in column (III), the metal used for metal complex formation in column (IV) the method of production according to one of the .Examples 1 to 5 in column (V) and the shade of the pad dyeings and prints on cotton (0) or wool (w) in column (VI).

Ere- 6 2-amino-l-hydroxy-Lchloroben- 1-amino-S-hydroxynaphthalene- 2.4.iytrichloropyrimidine Cr 2 Blue (c).

zene. 3.6-disulfnic acid. 00 3 Reddish blue (0). 7 Z-amindl-hydroxybenzene--suldo do CI 2 1118 (0).

ionig a)cid- -methyoxpropyl- O0 4 Reddish blue (0). ami e 8 2-amino-1-hydroxybenzenel-suldo do Cr 2 Blue (0).

ionic acid methylamide. Co 3 Redd sh blue (0). 9 do do 2.4.5.G-tetrachloropyrimidine C0 3 Reddlsh blue (W).

Cr 2 Blue (w). 10 2-a1nir1o-1-hydroxybenzene-l-suldo 5-br0mo-2.4.fi-triehloro-pyrimidine- Cr 2 lue (0).

innit:i acid-(2-hydroxy)-ethyl- Co 3 Reddish blue (0). am: e. 1l 2-amino-1-hydroxy-4-chloro-5- do 2.4.5.fitetrachloro-pyrimidine. Cr 2 Navy blue (0).

nitrobenzene. l2 2-amin0-1-hydroxy-4-eh10ro-6- do 2.4.6-tribromo-pyrimidine C1 2 D0.

nitrobenzene. 13 2-amino-1-hydroxy-4-nitrobenzene. d0 2.4.5.6-tetrachlor0-pyrimidine Cr 2 Greenlsh black (0). 14- 2-amin0-1-hydr0xy-4-chloro-6- do do C0 3 Reddlsh navy (c).

nitrobenzene. l5 2-amino-1-hydroxy-4.S-dinitrol-amin0-8-hydroxy-naphthalene- 2.4.5.6-tetrabromo-pyrimidine C0 3 Greenish black (0).

benzene. 3.6-disulf0nic acid. Cr 2 Blulsh black (0). 16 2-amin0-1-hydroxy-6-nitroben- 1-(3-amino)-benzoylamino-8-hy- 2.4.6-triehloro-pyrimidine. Cr 2 Navy b zene-i-sulfonic acid amide. droxy-n%)hthalene-3.6-disulionic aci 17 2-amino-l-hydroxy-4-chlorobenl-amino-8-hydroxy-naphthalene- 5-bromo-2A.G-trichloropyrimidine. Gr 2 N avyblue (c).

zene. 3.6-disu1fonic acid. 00 3 Reddlsh navy blue (0). Zamino-l-hydroxyA-nitr0benzene do do C1 2 Navy blue (0).

2-amin0-l-hydi'0xy-benzene-4sul- ..do 2.4.6-trichl0ropyrimidine C 2 Navyblue (W). ionic acid amide. Co 3 Reddish navy blue (w). 2-amino-l-hydroxy-4-nitr0benzene. l-amindS-hydroxy-naphthalenedo 1 l 4.6-disulfonic acid. A 00 5 Violet 2-am1no l-hydroxy-l-chloroben- 1-8511in0-8-hydr0xy-naphth3le11edo r 2 l zene. H 4.6-disulfonic acid. 3 vlolet (0 2-arnin0l-hydroxy-benzene-4suldo do Cr 2 Navy blue-(W) fonic acid am e. o do 2.4.5.6-tetrabromopyrimidine CI 2 Navy blue (0).

d0 do 2.4.&tribr0mopy1imidine C 2 (0 2-amm0-l-hydr0xy-4-chl0r0- 2-amino-8-hydroxy-naphthalene- 24.6-tribomopyrimidine C 3 V 016t (0). benzene. 3.6-disulf0nic acid. Cr 2 Do.

rln 2.4.5.6-tetrachloropyrimidiue (C30 2 101?; (c).

r o. 2-ei min0-1-l1ydroxy-4nitr0- do 2.4.6-trich1oropyrimidine Cr 2 Gray (0).

enzene. Q-amino-l-hydroxy-4-chloro-5- do 2.4.5.6-tetrachloropyrimidine Cr 2 Blllish g y nitrobenzene. 2-amino-l-hydroxy-4-ehloro-6- do do Cr 2 Violet (c).

nitrobenzene. 2-amin0-l-hydr0xy-4-cbloro-6- -.do 2.4.6-trichl0r0py'rimidne Cr 2 Violet (0).

nitrobenzene. 2-amino-l-hydr0xy-4-nitro-6- do 2.4.6-trich1or0pyrin1idine Cr 2 111 g y clilorobenzene. o do 2.4.5.(i-tetrachloropyrimidine Co 3 Reddish ray 2-amin0-1-hydroxy-4.6- dn rln Cr 2 Red-violet (c). 7 dinitrcbenzene. d0 dn 2.4.6-trichl0ropyrimidine Cr 1 Do.

2-amino-l-hydroxy-4-chlorol-aminO-S-hydroxy-naphthalenedo Or 2 Blue (0).

benzene. 2.4-disulf0nic acid. 2-ammc-l-hydroxy-4-nitro-6- 1-(4-amino)-benzoyl-aInino-8- 2.4.6-trichloropyrimidine Cr 2 Blue chlorobenzene. hydroxynaphthalene-3.fi-

disulfonic acid. 37 Z-ammo-l-hydr0xy-3.4.6-tr1chloro- 1-amino-8-hydroxynaphtha1ene- 2.4.5.6-tetrachlor0pyrimidine Cr 2 Navy blue (0).

benzene. 3.6-disulfonic acid. 38 2-amin0-l-hydroxy-4-nitrod 2.4.6-trichlor0pyrimidine. 3 Redd1shblaek(c).

benzene. 2 Greenish black (0). 39 2-amino-1-hydxoxy-4-bromol-amino-S-hydroxynaphthalene- 2.4.5.S-tetraehloropyrimidine Or 2 Blue (0).

benzene. 3.6-disulfonic acid Co 3 Reddish blue (c). 40.-." 2-amino-1-l1ydr0Xy-4-methyldo" 2.4.6-trichlor0pyrimidine Cr 2 Reddish blue (0). benzene. Co 3 Reddish blue (c). 41 2-amin0-l-hydroxy-4-1nethoxydo do Cr 2 Reddish blue (c). benzene. Co 3 Reddish blue (c). 42 2-amino-1-hydr0xy-6-acetylaminodo .....do Go 3 Reddish black (0). 4-nitrobenzene. Cr 2 Greenish black (0) 43 2-a.min0 l-hydroxy-e-methylsul- .d0 do Or 2 Blue (W).

fonylbenzene. Co 3 Reddish blue (W). 44... 2-amino-1-hydr0xy-benzene-4 .d0 2.4.5.fi-tetrachloropyrimidine Cr 2 Blue (W).

sulfonic acid phenylamide. Co 3 Reddish blue (w). 45.--" 2-amin0-1-hydroxybenzene-4- dn dn Cr 2 Blue (0).

sulfonic acid benzylamide. C0 3 Reddish blue (0). 46- 2axnin0-1-hydroxybenzene-4 1-amino-s-hydroxynaphthalene- 2.4.5.G-tetrachloropyrimidine Or 2 Blue (W).

sulfonic acid eyclohexylamide. 3.6-disulf0nic acid. Co 3 Reddish blue (w). 47 2-amin0-l-hydr0xy-4-ethylsuldo 2.4.5.6-tetrachl0ropyrimidine Cr 2 Blue (0).

fonylbenzene. Co 3 Reddish blue (0). 48 2-amino-l-hydr0xybenzene-4- do do Cr 2 Blue (0).

sulfonic acid ethylamide. C0 3 Reddish blue (0). 49- 2-amino-l-hydr0xybenzeneA- do do Cr 2 Blue (W).

sulfonic acid dimethylamide. I C0 3 Red sh blue (W). 50 2amino-Lhydroxybenzene-4- do do Or 2 Blue (0).

sulfonic acid-(3-hydroxy)- Co 3 Reddish blue (0). propylamide. 51 2-21.1nin0-1-l1ydroxy-4ethylbenzene d0 do Or 2 Reddish blue (c). 00 3 Reddish blue (0). 52 2-amino-l-hydroxy-4-nitr0-6- do do Cr 2 Blue (c).

carbethoxyaminobenzene. 53 2-amino-l-hydroxybenzene-4- do do Cr 2 Blue (w).

sulfenic acid-(2-carboxy)- phenylamide. 54 2-amino-1-hydroxy-4-nitro-6- do do Or 2 Reddish black (0).

benzoylaminobenzene. 55- 2-amino-l-hydroxy--nitro-G- 1-amino-Shydroxynaphthalene- 2.4.6-trichloropyrlmidine C1 2 Greenish black (0).

propiouylaminobenzene. 4.6-disulfonic acid. 56 Z-zgmino-l-hydroxydethoxydo do Or 2 Reddish blue (c).

enzene. 57 2-mino-l-hydroxybenzene-4- d0 2.4.5.G-tetrachloropyrimidine C0 4 Reddish blue (w).

sulfonic acid di-(2-l1ydroxyethyl)-amide.

Ex. (I) N o.

58 2-amino-l-hydroxybenzens- L Z-amino-B-hydroxynaphthalene- 2.4.5.6-tetrachloropyrimidine Cr 1 Blue (W).

sulfonic acid N-methyl-N- 3.6-disulfonic acid. phenylamide.

59---. zamino-l-hydroxybenzene-tl-amino-Ekhydroxynaphthalened Co 4 Reddish blue (W).

sulfonic acid diethylamide. 3.6-disulfonic acid.

60- 2-amino-1-hydroxybenzene-4- Lamina-8415;droxynaphthalenedo Cr 2 Blue (w).

sulfonic-acid N-2-hydroxy- 3.!rdisulfonic acid. ethyl-N-phenylamide.

61- 2-amino-l-hydroxybenzene-4- 1-(4-amino)-benzoylamino-& do Cr 2 Navy blue (0).

sulfonic acid di-(3-hydroxyhydroxynaphthalenw.G-disnlpropyD-amide. ionic acid.

62.--- 2-amin0-l-hydroxybenzene4- d0 do Cr 2 Navy blue (0).

sulfonic acid-(3'-su1famyl)- phenylamide.

63---. 2amino-1-hydr0xy-4-chloro-G- l-amino-8-hydroxynaphthalencdo Co 3 Reddish blue (0).

carbomethoxyaminobenzene. 4.6-disulfonic acid.

64 2-amino-l-hydroxybenzene-4- l-amino-S-hydroxynaphthalene- 2.4.6-tribromopyrimidine Cr 2 Blue (w).

sulfonic acid n-propylamide. 3.6-disuli0nic acid.

65- 2-amino-l-hydroxybenzene-4 1-amino 8hydroxynaphthalene- 2.4.5.fi-tetrabromopyrimidine Co 3 Reddish blue (c).

sulfonic acid-(2-eth0xy)- 3.6rdisulfonic acid. ethylamide.

66- Z-amino-l-hydroxybenzene-- 1-(3-amino)-benzoylamino-8- 2.4.6-trichloropyrimidine Cr 2 Blue (w).

sulionic acid-(4-methoxy)- hydroxynaphthalene-4.6-disulbutylamide. ionic acid.

67- zamino-l-hydroxybenzenei- 2-(4-amino)-benzoylamino-8- do Cr 2 Blue (0).

sulforiic acid-(4-methyl)- hydroxynaphthalenefi.6-disulcyclohexylamide. ionic acid.

68- r 2-amino-1-hydroxybenzenek 1-amin0-8-hydroxynaphthalenecl0 Cr 2 Blue (0).

sulionic acid-(2-methoxy)- 3.6-disulfonic acid. phenylamide.

69- z-amino-l-hydroxybenzcneido do Cr 2 Blue (0).

sulfonic acid-(3-chloro)- phenylamide.

70 2-amir10-l-hydroxybenzene-4- d0 do Cr 2 Blue (c).

sulfonic acid-(4-methyl)- phenylamlde.

Formulae of representative dyestuffs of the foregoing EXAMPLE 4 exam les are as follows:

p OzN O EXAMPLE 1 H038 by l I ll 00 13+ 0 H0318 IL o H NH I 110 s NH- I L 01 N 2 H038 l Cl N 2 EXAMPLE 5 EXAMPLE 2 x r O1 0 OzN N N Go H+ I! Cr 11+ H038 0 NH- NH H 01 HO l -c1 3 H038 i C} l 01 01 h k \N/ J 2 EXAMPLE 3 EXAMPLE 6 (FIRST DYESTUFF) (.N ofi x l Cl 0-- N N Go H+ N H033 N 1% CO EU I H0 I I NEE-- 01 NH- 11038 1 01 HO 3 N c1 l J2 q 10 EXAMPLE 6 (SECOND DYESTUFF) I l i ll Cr H+ I NH- -0i Hogs EXAMPLE C2H4OH 1P1 C0 H+ t I I NH -o1 1103s I k \N/ ,)2

EXAMPLE 13 ll Cr H+ H033 N NH Cl 1 N o1 H038 EXAMPLE 38 (FIRST DYESTUFF) OiNQO [I Go H+ H033 I? I l NH H HOaS mclTci N J2 4 EXAMPLE 3s (SECOND DYESTUFF) H Cr H+ H035 N l NH- H Ross 1 T Having thus disclosed the invention what we claim is: l. A member selected from the group consisting of the 75 1:2-chromium and the 1:2-cobalt complex compounds of the dyestufi of the formula I OH NH- -00 x g;- N a N NH ml wherein X is the polyhalogenopyrimidyl radical of the formula hal being a halogen atom with an atomic number from 17 to 35, inclusive,

and Y being a member selected from the group consisting of hydrogen, chlorine and bromine,

w is a member selected from the group consisting of hydrogen and chlorine,

is a member selected from the group consisting of hydrogen, chlorine. .and I 1it,r9,

is a member selected from the group consisting of chlorine, bromine, nitro, lower alkyl, lower alkoxy,

' lower alkanoylamino, lower carboalkoxyamino, benand .lower alkylphenylamide, sulfonic acid lower alkoxyphenylamide and sulfonic acid chlorophenylamide,

n is one of the integers 1 and 2, the group stands in one of the positions 7 and 8 of the naphthalene nucleus, and the group, -NH stands in one of the positions 3 and 4.

NH X

2. The cobalt-containing reactive dyestuff of the formula 15 3. The chromium-containing reactive dyestufi? of the fcrmula formula l 1 lm 6. The cobalt-containing reactive dyestuff of the formula HO IS 4. The cobalt-containing reactive dyestuif of the for- A 5. The chromium-containing reactive dyestuff of the 16 7. The chromium-containing reactive dyestuif of the formula C: H!- H021S H (1 L N J 8. The cobalt-containing reactive dyestuff of the formula -r'QflqQQ 1 N O H+ H0 8 I I o 01 1 C1 LL \N/ G1 J2 9. The chromium-containing reactive dyestuif of the formula -"O,N O C H References Cited by the Examiner UNITED STATES PATENTS H 1,667,312 4/1928 Fritzsche et a1 260153 1,886,480 11/1932 Hailer et a1. 260146 3,125,564 3/1964 Heslop et a1 260153 FOREIGN PATENTS 569,115 1/1959 Belgium. 1,221,621 1/1960 France. 1,225,281 2/1960 France.

CHARLES B. PARKER, Primary Examiner.

R. I. FINNEGAN, Assistant Examiner. 

1. A MEMBER SELECTED FROM THE GROUP CONSISTING OF THE 1:2-CHROMINUM AND THE 1:2-COBALT COMPLEX COMPOUNDS OF THE DYESTUFF OF THE FORMULA 